Isothiazole and Isoxazole derivatives

ABSTRACT

Microbicidal substituted pyrazolin-5-ones of the formula ##STR1## in which R 1  and R 2  independently of one another each represent hydrogen, alkyl, alkenyl, alkinyl, cyanoalkyl, hydroxyalkyl, alkoxyalkyl, alkylthioalkyl, alkoxycarbonyl, hydroxycarbonylalkyl, alkoxycarbonylalkyl, aminocarbonylalkyl, alkyllaminocarbonylalkyl or dialkylaminocarbonylalkyl, or represent in each case optionally substituted oxiranylalkyl, aralkyl, heterocyclyl or aryl and 
     Het represents an optionally substituted heterocyclic radical. 
     Intermediates therefor of the formula ##STR2## in which R is alkyl, are also new.

This is a division of application Ser. No. 890,245, filed July 24, 1986,now U.S. Pat. No. 4,767,775.

The invention relates to new substituted pyrazolin-5-ones, severalprocesses for their preparation and their use as agents for combatingpests.

It is already known that organic nitrogen compounds, such as, forexample, zinc ethylene-1,2-bis-(dithiocarbamate) have fungicidalproperties (compare, for example, R. Wegler "Chemie derPflanzenschutz-und Schadlingsbekampfungsmittel" ("Chemistry of PlantProtection Agents and Agents for Combating Pests"), Springer VerlagBerlin, Heidelberg, New York 1970, Volume 2, page 65 et seq.).

The action of these compounds, however, is not always completelysatisfactory in all fields of use, especially when low amounts andconcentrations are applied.

New substituted pyrazolin-5-ones of the general formula (I) ##STR3## inwhich

R¹ and R² independently of one another each represent hydrogen, alkyl,alkenyl, alkinyl, cyanoalkyl, hydroxyalkyl, alkoxyalkyl, alkylthioalkyl,alkoxycarbonyl, hydroxycarbonylalkyl, alkoxycarbonylalkyl,aminocarbonylalkyl, alkylaminocarbonylalkyl ordialkylaminocarbonylalkyl, or represent in each case optionallysubstituted oxiranylalkyl, aralkyl, heterocyclyl or aryl and Hetrepresents an optionally substituted heterocyclic radical, have beenfound.

The compounds of the formula (I) can exist as geometric isomers orisomer mixtures of different composition. Both the pure isomers and theisomer mixtures are claimed according to the invention.

It has furthermore been found that the new substituted pyrazolin-5-onesof the general formula (I) ##STR4## in which

R¹ and R² independently of one another each represent hydrogen, alkyl,alkenyl, alkinyl, cyanoalkyl, hydroxyalkyl, alkoxyalkyl, alkylthioalkyl,alkoxycarbonyl, hydroxycarbonylalkyl, alkoxycarbonylalkyl,aminocarbonylalkyl, alkylaminocarbonylalkyl ordialkylaminocarbonylalkyl, or represent in each case optionallysubstituted oxiranylalkyl, aralkyl, heterocyclyl or aryl and Hetrepresents an optionally substituted heterocyclic radical,

are obtained by a process in which

(a) 4-oximino-pyrazolin-5-ones of the formula (II) ##STR5## in which

R¹ and R² have the abovementioned meaning and A represents hydrogen oran alkali metal cation, are reacted with alkylating agents of theformula (III)

    Het--CH.sub.2 --X                                          (III)

in which

Het has the abovementioned meaning and X represents anelectron-withdrawing leaving group,

if appropriate in the presence of a diluent, if appropriate in thepresence of an acid-binding agent and if appropriate in the presence ofa catalyst, or in which (b) the alkoximinocarboxylic acid esters of theformula (IV) ##STR6## in which R represents alkyl and R¹ and Het havethe abovementioned meaning,

are reacted with hydrazine derivatives of the formula (V)

    R.sup.2 --NH--NH.sub.2                                     (V)

in which

R² has the abovementioned meaning, if appropriate in the presence of adiluent, or in which (c) the 4-alkoximino-pyrazolin-5-ones obtainable byprocess (a) or by process (b), of the formula (Ia) ##STR7## in which

R¹ and Het have the abovementioned meaning, are reacted with alkylatingagents of the formula (VI)

    R.sup.2' --Y                                               (VI)

in which R^(2') represents alkyl, alkenyl, alkinyl, cyanoalkyl,hydroxyalkyl, alkoxyalkyl, alkylthioalkyl, hydroxycarbonylalkyl oralkoxycarbonylalkyl, or represents in each case optionally substitutedaralkyl or heterocyclyl and Y represents an electron-withdrawing leavinggroup,

if appropriate in the presence of a diluent, if appropriate in thepresence of an acid-binding agent and if appropriate in the presence ofa catalyst.

Finally, it has been found that the new substituted pyrazolin-5-ones ofthe formula (I) have fungicidal and bactericidal properties.

Surprisingly, the new substituted pyrazolin-5-ones of the formula (I)exhibit better fungicidal properties than zincethylene-1,2-bis-dithiocarbamate, which is known from the prior art andis a closely related compound from the point of view of its action.

Formula (I) provides a general definition of the substitutedpyrazolin-5-ones according to the invention. Preferred compounds of theformula (I) are those in which

R¹ and R² independently of one another each represent hydrogen, orrepresent in each case straight-chain or branched alkyl, alkenyl,alkinyl, cyanoalkyl, hydroxyalkyl, alkoxyalkyl, alkylthioalkyl,alkoxycarbonyl, hydroxycarbonylalkyl, alkoxycarbonylalkyl,aminocarbonylalkyl, alkylaminocarbonylalkyl or dialkylaminocarbonylalkylwith in each case up to 8 carbon atoms in the individual alkyl, alkenylor alkinyl parts, or represent oxiranylalkyl with 1 to 4 carbon atoms inthe straight-chain or branched alkyl part, or represent1,1-dioxotetrahydrothienyl, or represent straight-chain or branchedaralkyl which has 1 to 4 carbon atoms in the alkyl part and 6 to 10carbon atoms in the aryl part and is optionally monosubstituted orpolysubstituted by identical or different substituents, or representaryl which has 6 to 10 carbon atoms and is optionally monosubstituted orpolysubstituted by identical or different substituents, possiblesubstituents in the aryl part in each case being: halogen, cyano, nitro,hydroxyl, in each case straight-chain or branched alkyl, alkoxy,dioxyalkylene, alkylcarbonyloxy and alkylthio with in each case up to 4carbon atoms, straight-chain or branched halogenoalkyl, halogenoalkoxyand halogenoalkylthio with in each case up to 4 carbon atoms and up to 9identical or different halogen atoms and phenyl

and

Het represents a saturated or unsaturated five-membered or six-memberedheterocyclic radical which has one to 3 heteroatoms, in particularnitrogen, oxygen and/or sulphur, and is optionally monosubstituted orpolysubstituted by identical or different substituents and/obenzo-fused, possible substituents being: hydroxyl, halogen, cyano,nitro, in each case straight-chain or branched alkyl, alkoxy andhalogenoalkyl with in each case 1 to 4 carbon atoms and, in the case ofthe halogenoalkyl 1 to 9 identical or different halogen atoms and phenylwhich is optionally monosubstituted or polysubstituted by identical ordifferent substituents from the group comprising lower alkyl, loweralkoxy, halogen and/or nitro. Particularly preferred compounds of theformula (I) are those in which

R¹ and R² independently of one another in each case represent hydrogen,methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, allyl, butenyl,propargyl, cyanomethyl, cyanoethyl, hydroxymethyl, hydroxyethyl,methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl,methylthiomethyl, methoxycarbonyl, ethoxycarbonyl,hydroxycarbonylmethyl, hydroxycarbonylethyl, methoxycarbonylmethyl,methoxycarbonylethyl, ethoxycarbonylmethyl, ethoxycarbonylethyl,aminocarbonylmethyl, methylaminocarbonylmethyl,ethylaminocarbonylmethyl, dimethylaminocarbonylmethyl,diethylaminocarbonylmethyl, aminocarbonylethyl, oxiranylmethyl oroxiranylethyl, or represent 1,1-dioxotetrahydrothien-3-yl, or representphenyl or benzyl which is optionally mono-, di- or trisubstituted byidentical or different substituents, possible substituents being:fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxyl, methyl,ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy,dioxymethylene, dioxyethylene, methylthio, ethylthio, acetoxy andpropionyloxy, chloromethyl, dichloromethyl, trichloromethyl,trifluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl,trifluoromethoxy, trifluoromethylthio and phenyl and Het represents aheterocyclic radical of the formula ##STR8## which is optionally mono-,di- or trisubstituted by identical or different substituents and/orbenzo-fused, possible substituents in each case being: fluorine,chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,methoxy, ethoxy, trifluoromethyl and phenyl which is optionally mono-,di- or trisubstituted by identical or different substituents from thegroup comprising chlorine, nitro, methyl and/or methoxy and

wherein

X in each case represents oxygen or sulphur.

The compounds listed by name in the preparation examples may bementioned specifically.

If, for example, 4-hydroximino-1,3-dimethyl-pyrazolin-5-one and3-methyl-5-chloromethyl-1,2-oxazole are used as starting substances, thecourse of the reaction in process (a) according to the invention can berepresented by the following equation: ##STR9##

If, for example, ethylβ-keto-α-[(3-ethylisoxazol-5-yl)-methoximino]-butyrate and hydrazinehydrate are used as starting substances, the cause of the reaction inprocess (b) according to the invention can be represented by thefollowing equation: ##STR10##

If, for example,4-(benzoxazol-2-ylmethyl-oximino)-3-methyl-pyrazolin-5-one andchloroacetonitrile are used as starting substances, the course of thereaction in process (c) according to the invention can be represented bythe following equation: ##STR11##

Formula (II) provides a general definition of the4-oximino-pyrazolin-5-ones required as starting substances for carryingout process (a) according to the invention. In this formula (II), R¹ andR² preferably represent those radicals which have already been mentionedfor this substituent in the description of the substances of the formula(I) according to the invention. A preferably represents hydrogen, orrepresents a sodium or potassium cation.

The 4-oximino-pyrazolin-5-ones of the formula (II) are known in somecases [compare, for example, Ber. dtsch. chem. Ges. 29, 249 (1986);Coll. Czech. Chem. Commun. 25, 55 (1960); Arch. Pharm. 309, 900 (1976);and Liebigs Ann. Chem. 1976, 1390].

They are obtained, for example, by a process in which β-keto esters ofthe formula (VII) ##STR12## in which

R¹ has the abovementioned meaning and R⁴ represents lower alkyl, inparticular methyl or ethyl, or in which ethoxymethylenemalonates of theformula (VIII) ##STR13## are initially hydrolyzed in a 1st stage withhydrazines of the formula (V)

    R.sup.2 --NH--NH.sub.2                                     (V)

in which

R² has the abovementioned meaning, if appropriate in the presence of adiluent, such as, for example, ethanol, at temperatures between 0° C.and 100° C., the 4-ethoxycarbonylpyrazolin-5-ones resulting from themalonate of the formula (VIII), of the formula (IX) ##STR14## in which

R² has the abovementioned meaning, are hydrolyzed and decarboxylated inan intermediate step by customary methods, for example with aqueoushydrochloric acid at temperatures between 50° C. and 120° C., and thepyrazolin-5-ones thus obtainable, of the formula (X) ##STR15## in which

R¹ and R² have the abovementioned meaning, are reacted in a 2nd stage(or 3rd stage) with a nitrosating agent, such as, for example, isopentylnitrite or sodium nitrite, if appropriate in the presence of a diluent,such as, for example, ethanol, water or aqueous hydrochloric acid, andif appropriate in the presence of a base, such as, for example, sodiummethylate, at temperatures between -20° C. and +50° C.

Formula (III) provides a general definition of the alkylating agentsrequired as starting substances for carrying out process (a) accordingto the invention. In this formula (III), Het represents those radicalswhich have already been mentioned for these substituents in connectionwith the description of the substances of the formula (I) according tothe invention. X preferably represents halogen, in particular chlorine,bromine or iodine, or represents optionally substitutedalkylsulphonyloxy, alkoxysulphonyloxy or arylsulphonyloxy, such as, forexample, methanesulphonyloxy, methoxysulphonyloxy,trifluoromethanesulphonyloxy or p-toluenesulphonyloxy.

The alkylating agents of the formula (III) are generally known compoundsof organic chemistry.

The β-keto esters of the formula (VII) and the ethoxymethylenemalonatesof the formula (VIII) are likewise generally known.

Formula (IV) provides a general definition of the alkoximinocarboxylicacid esters required as starting substances for carrying out process (b)according to the invention. In this formula (IV), R¹ and Het representthose radicals which have already been mentioned for these substituentsin connection with the description of the substances of the formula (I)according to the invention. R preferably represents straight-chain orbranched alkyl with 1 to 4 carbon atoms, in particular methyl or ethyl.

The alkoximinocarboxylic acid esters of the formula (IV) are not yetknown.

They are obtained by a process in which hydroximinocarboxylic acidesters of the formula (XI) ##STR16## in which

R and R¹ have the abovementioned meaning, are reacted with alkylatingagents of the formula (III)

    Het--CH.sub.2 --X                                          (III)

in which

Het has the abovementioned meaning and X represents anelectron-withdrawing leaving group, in particular chlorine, bromine oriodine, or represents optionally substituted alkylsulphonyloxy,alkoxysulphonyloxy or arylsulphonyloxy, such as, for example,methanesulphonyloxy, methoxysulphonyloxy, trifluoromethanesulphonyloxyor p-toluenesulphonyloxy,

if appropriate in the presence of a diluent, such as, for example,acetonitrile, and if appropriate in the presence of an acid-bindingagent, such as, for example, triethylamine, at temperatures between +10°C. and +80° C.

The hydroximinocarboxylic acid esters of the formula (XI) are generallyknown compounds of organic chemistry (compare, for example, Helv. Chim.Acta 67, 906-915 [1984]; French patent application No. 2,434,572;Yakugaku Zasshi 87, 1209-1211 [1967] or Chem. Ber. 100, 1245-1247[1967]).

Formula (la) provides a general definition of the4-alkoximinopyrazolin-5-ones required as starting substances forcarrying out process (c) according to the invention. In this formula(Ia), R¹ and Het preferably represent those radicals which have alreadybeen mentioned for these substituents in connection with the descriptionof the substances of the formula (I) according to the invention.

The 4-alkoxyiminopyrazolin-5-ones of the formula (Ia) are compoundsaccording to the invention and are obtainable with the aid of processes(a) or (b) according to the invention.

Formula (VI) provides a general definition of the alkylating agentsfurthermore required as starting substances for carrying out process (c)according to the invention. In this formula (VI), R^(2') preferablyrepresents those radicals which have already been mentioned for thesubstituent R² in connection with the description of the substances ofthe formula (I) according to the invention, with the exception of thehydrogen radical and the optionally substituted aryl radicals. Ypreferably represents those leaving groups which have already beenmentioned for the substituent X in the description of the alkylatingagents of the formula (III).

The alkylating agents of the formula (VI) are likewise generally knowncompounds of organic chemistry.

Possible diluents for carrying out process (a) according to theinvention are inert organic solvents or aqueous systems.

These include, in particular, aliphatic or aromatic, optionallyhalogenated hydrocarbons, such as, for example, benzine, benzene,toluene, xylene, chlorobenzene, petroleum ether, hexane, cyclohexane,methylene chloride, chloroform and carbon tetrachloride; ethers, such asdiethyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl ordiethyl ether; ketones, such as acetone or butanone; nitriles, such asacetonitrile or propionitrile; amides, such as dimethylformamide,dimethylacetamide, N-methylformanilide, N-methylpyrrolidone orhexamethylphosphoric acid triamide; esters, such as ethyl acetate;sulphoxides, such as dimethylsulphoxide, or also water oraqueous-organic two-phase mixtures, such as methylene chloride/water ortoluene/water.

If appropriate, process (a) according to the invention is carried out inthe presence of an acid-binding agent. Possible acid-binding agents areall the customary inorganic or organic bases. These include, forexample, alkali metal hydroxides, amides, alcoholates or hydrides, suchas sodium hydroxide or potassium hydroxide, sodium methylate orpotassium t-butylate, sodium hydride or sodium amide; alkali metalcarbonates, such as sodium carbonate, potassium carbonate or sodiumbicarbonate, and tertiary amines, such as triethylamine,N,N-dimethylaniline, pyridine, N,N-dimethylaminopyridine,diazabicyclooctane (DABCO), diazabicyclononene (DBN) ordiazabicycloundecene (DBU).

The reaction temperature can be varied within a substantial range incarrying out process (a) according to the invention. The reaction is ingeneral carried out at temperatures between -20° C. and +200° C.,preferably at temperatures between 0° C. and +150° C.

In carrying out process (a) according to the invention, in general 1.0to 3.0 moles, preferably 1.0 to 1.5 moles, of alkylating agent of theformula (III) and, if appropriate, 1.0 to 3.0 moles, preferably 1.0 to1.5 moles, of acid-binding agent are employed per mole of4-oximino-pyrazolin-5-one of the formula (II).

If an organic-aqueous two-phase system is used, the reaction can becarried out, if appropriate, in the presence of 0.1 to 1 mole of asuitable phase transfer catalyst, such as, for example, a quaternaryammonium or phosphonium compound. Examples which may be mentioned aetriethylbenzylammonium chloride and benzyl-dodecyldimethylammoniumchloride.

The reaction products of the formula (I) are worked up and isolated bycustomary methods.

Possible diluents for carrying out process (b) according to theinvention are likewise inert organic solvents.

These include, in particular, aliphatic or aromatic, optionallyhalogenated hydrocarbons, such as, for example, benzine, benzene,toluene, xylene, chlorobenzene, petroleum ether, hexane, cyclohexane,methylene chloride, chloroform and carbon tetrachloride; ethers, such asdiethyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl ordiethyl ether, or alcohols, such as methanol, ethanol or propanol.

The reaction temperatures can be varied within a substantial range incarrying out process (b) according to the invention. The reaction is ingeneral carried out at temperatures between 0° C. and 150° C.,preferably at temperatures between 20° C. and 120° C.

For carrying out process (b) according to the invention, in general 0.8to 2.5 moles, preferably 1.0 to 1.2 moles, of hydrazine derivative ofthe formula (V) are employed per mole of alkoximinocarboxylic acid esterof the formula (IV). The reaction is carried out and the reactionproducts of the formula (I) are worked up and isolated by customarymethods.

Possible diluents for carrying out process (c) according to theinvention are likewise inert organic solvents or aqueous systems. Theorganic solvents or aqueous-organic two-phase mixtures mentioned forprocess (a) are preferably used.

If appropriate, process (c) according to the invention is carried out inthe presence of an acid-binding agent. Acid-binding agent which arepreferably used are the inorganic or organic bases mentioned for process(a).

The reaction temperatures can likewise be varied within a substantialrange in carrying out process (c) according to the invention. Thereaction is in general carried out at temperatures between -20° C. and+200° C., preferably at temperatures between 0° C. and +150° C.

In carrying out process (c) according to the invention, in general 1.0to 3.0 moles, preferably 1.0 to 1.5 moles, of alkylating agent of theformula (VI) and, if appropriate, 0.5 to 3.0 moles, preferably 0.6 to1.5 moles, of acid-binding agent are employed per mole of4-alkoximino-pyrazolin-5-one of the formula (Ia).

The reaction is carried out and the reaction products of the formula (I)are worked up and isolated as described for process (a) or by generallycustomary processes.

The active compounds according to the invention exhibit a powerfulmicrobicidal action and can be employed in practice for combatingundesired microorganisms. The active compounds are suitable for use asplant protection agents.

Fungicidal agents in plant protection are employed for combatingPlasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes,Ascomycetes, Basidiomycetes and Deteromycetes.

Bactericidal agents are used in plant protection for combatingPseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceaeand Streptomycetaceae.

Some causative organisms of fungal and bacterial diseases which comeunder the generic names listed above may be mentioned as examples, butnot by way of limitation: Xanthomonas species, such as, for example,Xanthomonas campestris pv. oryzae; Pseudomonas species, such as, forexample, Pseudomonas syringae pv. lachrymans; Erwinia species, such as,for example, Erwinia amylovora; Pythium species, such as, for example,Pythium ultimum; Phytophthora species, such as, for example,Phytophthora infestans; Pseudoperonospora species, such as, for example,Pseudoperonospora humuli or Pseudoperonospora cubense; Plasmoparaspecies, such as, for example, Plasmopara viticola; Peronospora species,such as, for example, Peronospora pisi or P. brassicae; Erysiphespecies, such as, for example, Erysiphe graminis; Sphaerotheca species,such as, for example, Sphaerotheca fuliginea; Podosphaera species, suchas, for example, Podosphaera leucotricha; Venturia species, such as, forexample, Venturia inaequalis; Pyrenophora species, such as, for example,Pyrenophora teres or P. graminea, (conidia form: Drechslera, Syn:Helminthosporium); Cochliobolus species, such as, for example,Cochliobolus sativus (conidia form: Drechslera, syn: Helminthosporium);Uromyces species, such as, for example, Uromyces appendiculatus;Puccinia species, such as, for example, Puccinia recondita; Tilletiaspecies, such as, for example, Tilletia caries; Ustilago species, suchas, for example, Ustilago nuda or Ustilago avenae; Pellicularia species,such as, for example, Pellicularia sasakii; Pyricularia species, suchas, for example, Pyricularia oryzae; Fusarium species, such as, forexample, Fusarium culmorum; Botrytis species, such as, for example,Botrytis cinerea; Septoria species, such as, for example, Septorianodorum; Leptosphaeria species, such as, for example, Leptosphaerianodorum; Cercospora species, such as, for example, Cercospora canescens;Alternaria species, such as, for example, Alternaria brassicae; andPseudocercosporella species, such as, for example, Pseudocercosporellaherpotrichoides.

The good toleration, by plants, of the active compounds, at theconcentrations required for combating plant diseases, permits treatmentof above-ground parts of plants, of vegetative propagation stock andseeds; and of the soil.

The active compounds according to the invention can be used here withparticularly good success for combating cereal diseases caused, forexample, by Chochliobolus sativus, Leptosphaeria nodorum, Erysiphegraminis or Pyrenophora teres, for combating vegetable diseases caused,for example, by the causative organism of brown rot of tomato(Phytophthora infestans), or for combating rice diseases, such as, forexample, against the causative organism of rice spot disease(Pyricularia oryzae) or against the causative organism Pelliculariasasakii. The active compounds according to the invention thereby alsoshow, in addition to a protective activity, systemic properties, andfurthermore also a good activity against the bacterial disease Erwiniaamylovora (fire blight). The fungicidal activity of the compoundsaccording to the invention is also found in vitro in the agar platetest.

Besides an outstanding protective activity, the active compoundsaccording to the invention also exhibit very good systemic properties.They are distinguished by a broad fungicidal in vitro action and byadditional bactericidal properties.

The active compounds can be converted to the customary formulations,such as solutions, emulsions, suspensions, powders, dusts, foams,pastes, soluble powders, granules, aerosols, suspension-emulsionconcentrates, seed treatment powders, natural and synthetic materialsimpregnated with active compound, very fine capsules in polymericsubstances and in coating compositions for seed, and formulations usedwith burning equipment, such as fumigating cartridges, fumigating cans,fumigating coils and the like, as well as ULV cold mist and warm mistformulations.

These formulations are produced in known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents, liquefiedgases under pressure, and/or solid carriers, optionally with the use ofsurface-active agents, that is, emulsifying agents and/or dispersingagents, and/or foam-forming agents. In the case of the use of water asan extender, organic solvents can, for example, also be used asauxiliary solvents. As liquid solvents, there are suitable in the main:aromatics, such as xylene, toluene or alkyl naphthalenes, chlorinatedaromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes,chloroethylenes or methylene chloride, aliphatic hydrocarbons, such ascyclohexane or paraffins, for example mineral oil fractions, alcohols,such as butanol or glycol as well as their ethers and esters, ketones,such as acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethylsulphoxide, as well as water. By liquefied gaseous extenders orcarriers are meant liquids which are gaseous at normal temperature andunder normal pressure, for example aerosol propellants, such ashalogenated hydrocarbons as well as butane, propane, nitrogen and carbondioxide. As solid carriers there are suitable: for example groundnatural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticmaterials, such as highly-dispersed silicic acid, alumina and silicates.As solid carriers for granules there are suitable: for example crushedand fractionated natural rocks such as calcite, marble, pumice,sepiolite and dolomite, as well as synthetic granules of inorganic andorganic meals, and granules of organic material such as sawdust, coconutshells, corn cobs and tobacco stalks; as emulsifying and/or foam-formingagents there are suitable: for example non-ionic or anionic emulsifiers,such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcoholethers, for example alkylaryl polyglycol ethers, alkyl sulphonates,alkyl sulphates, aryl sulphonates as well as albumin hydrolysisproducts; as dispersing agents there are suitable: for exampleligninsulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules and latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 percent by weightof active compound, preferably between 0.5 and 90%.

The active compounds according to the invention can be present in theformulations as a mixture with other known active compounds, such asfungicides, insecticides, acaricides and herbicides, and in mixtureswith fertilizers and growth regulators.

The active compounds can be used as such or in the form of theirformulations or the use forms prepared therefrom, such as ready-to-usesolutions, suspensions, wettable powders, pastes, soluble powders, dustsand granules. They are used in the customary manner, for example bywatering, spraying, atomizing, scattering, dusting, foaming, brushing onand the like. It is furthermore possible to apply the active compoundsby the ultra-low volume method or to inject the active compoundformulation or the active compound itself into the soil. The seed of theplants can also be treated.

In the treatment of parts of plants, the active compound concentrationsin the use forms can be varied within a substantial range. They are, ingeneral, between 1 and 0.0001% by weight, preferably between 0.5 and0.001%.

In the treatment of seed, amounts of active compound of 0.001 to 50 gper kilogram of seed, preferably 0.01 to 10 g, are generally required.

For the treatment of soil, active compound concentrations of 0.00001 to0.1% by weight, preferably 0.0001 to 0.02% by weight, are required atthe place of action.

PREPARATION EXAMPLES Example 1 ##STR17##

First 11.1 g (0.11 mole) of triethylamine and then, dropwise, 11.35 g(0.085 mole) of 3-methyl-5-chloromethyl-1,2,4-oxadiazole are added to 12g (0.085 mole) of 1,3-dimethyl-4-hydroximino-pyrazolin-5-one in 100 mlof acetonitrile, while stirring. When the addition has ended, themixture is warmed at 50° C. for one hour, the solvent is removed invacuo, the residue is taken up in chloroform, the mixture is washedseveral times with water and dried over magnesium sulphate and thesolvent is removed in vacuo. The oil which remains is purified bychromatography (silica gel/mobile phase; chloroform/ether 10:1) and theproduct is crystallized from petroleum ether.

9.9 g (49% of theory) of4-[(3-methyl-1,2,4-oxadiazol-5-yl)-methoximino]-1,3-dimethyl-pyrazolin-5-oneof melting point 54° C. are obtained.

Preparation of the starting compound ##STR18##

183 g (1.56 moles) of isopentyl nitrite are added dropwise to 175 g(1.56 moles) of 1,3-dimethyl-pyrazolin-5-one and 84.4 g (1.56 moles) ofsodium methylate in 1 l of aboslute ethanol, while stirring and coolingwith ice, so that the internal temperature does not exceed 25° C. to 30°C. When the addition has ended, the mixture is stirred at roomtemperature for a further 24 hours and the sodium salt of1,3-dimethyl-4-hydroximino-pyrazolin-5-one which has precipitated out isfiltered off with suction. The crystalline product is dissolved in 1 lof water and acidified with glacial acetic acid. For completeprecipitation, the mixture is cooled at 0° C. for several hours and theproduct is then filtered off with suction.

162 g (74% of theory) of 1,3-dimethyl-4-hydroximino-pyrazolin-5-one ofmelting point 93° C. are obtained.

Example 2 ##STR19##

320 g (1.194 moles) of ethylβ-keto-α-[(3-ethylisoxazol-5-yl)-methoximino]-butyrate in 400 ml ofethanol are warmed to 70° C. dropwise with 59.5 g (1.19 moles) ofhydrazine hydrate at room temperature, while stirring. When the additionhas ended, stirring is continued at the reflux temperature for a further3 hours and the solvent is then distilled off from the cooled reactionmixture under reduced pressure. The residue, which crystallizes whenstirred with ethanol/diethyl ether, is filtered off with suction anddried.

205 g (73% of theory) of4-[(3-ethylisoxazol-5-yl)-methoximino]-3-methyl-pyrazolin-5-one ofmelting point 118° C. are obtained.

Example 3 ##STR20##

205 g (0.869 mole) of4-[3-ethylisoxazol-5-yl)-methoximino]-3-methyl-pyrazolin-5-one, 82.8 g(0.6 mole) of powdered potassium carbonate and 63.4 ml (1 mole) ofchloroacetonitrile in 1,000 ml of acetone are heated under reflux for 4hours. Thereafter, a further 21.1 ml (0.33 mole) of chloroacetonitrileare added and the mixture is heated under reflux for a further 2 hours.The cooled reaction mixture is concentrated in vacuo, the residue istaken up in methylene chloride, the insoluble constituents are filteredoff, the filtrate is washed several times, dried over sodium sulphateand concentrated in vacuo and the residue is purified by chromatography(silica gel).

74.3 g (35% of theory) of1-cyanomethyl-4-[(3-ethylisoxazol-5-yl)-methoximino]-3-methyl-pyrazolin-5-oneare obtained as an oil.

¹ H-NMR (CDCl₃ /tetramethylsilane as the internal standard): δ=5.5 ppm(═N--O--CH₂ --)

The following substituted pyrazolin-5-ones of the general formula (I)are obtained in a corresponding manner and in accordance with thegeneral statements on the preparation: ##STR21##

                                      TABLE 1                                     __________________________________________________________________________    Example                                    Physical                           No.  R.sup.1   R.sup.2     Het             data                               __________________________________________________________________________    4    H         CH.sub.3                                                                                                  Melting point 146°-148.d                                               egree. C.                          5    CH.sub.3  H                                                                                          ##STR22##      Melting point 135° C.       6    CH.sub.3  CH.sub.3                                                                                   ##STR23##      Melting point 101° C.       7    CH.sub.3  (CH.sub.3).sub.3 C                                                                         ##STR24##      .sup.1 HNMR* 5.41 ppm              8    CH.sub.3  CH.sub.2CHCH.sub.2                                                                         ##STR25##      .sup.1 HNMR* 5.45 ppm              9    CH.sub.3  NCCH.sub.2                                                                                 ##STR26##      .sup.1 HNMR* 5.5 pmm               10   CH.sub.3  HOCH.sub.2CH.sub.2                                                                         ##STR27##      .sup.1 HNMR* 5.5 ppm               11   CH.sub.3  CH.sub.3 OCOCH.sub.2                                                                       ##STR28##      .sup.1 HNMR* 5.6 ppm               12   CH.sub.3                                                                                 ##STR29##                                                                                 ##STR30##      .sup.1 HNMR* 5.0 ppm               13   CH.sub.3                                                                                 ##STR31##                                                                                 ##STR32##      .sup.1 HNMR* 5.5 ppm               14   CH.sub.3                                                                                 ##STR33##                                                                                 ##STR34##      Melting point 180° C.                                                  (decomposition)                    15   CH.sub.3                                                                                 ##STR35##                                                                                 ##STR36##      Melting point 104° C.       16   C.sub.2 H.sub.5                                                                         CH.sub.3                                                                                   ##STR37##      .sup.1 HNMR* 5.5 ppm               17   CH.sub.3(CH.sub.2).sub.2                                                                CH.sub.3                                                                                   ##STR38##      .sup.1 HNMR* 5.46 ppm              18   (CH.sub.3).sub.3 C                                                                      CH.sub.3                                                                                   ##STR39##      Melting point 73° C.        19                                                                                  ##STR40##                                                                              CH.sub.3                                                                                   ##STR41##      Melting point 100° C.       20                                                                                  ##STR42##                                                                              CH.sub.3                                                                                   ##STR43##      Melting point 83° C.        21   CH.sub.3  CH.sub.3                                                                                   ##STR44##      .sup.1 HNMR* 5.5 ppm               22   CH.sub.3  (CH.sub.3).sub.3 C                                                                         ##STR45##      .sup.1 HNMR* 5.4 ppm               23   CH.sub.3  HOCH.sub.2CH.sub.2                                                                         ##STR46##      .sup.1 HNMR* 5.5 ppm               24   CH.sub.3                                                                                 ##STR47##                                                                                 ##STR48##      .sup. 1 HNMR* 5.0 ppm              25   CH.sub.3                                                                                 ##STR49##                                                                                 ##STR50##      .sup.1 HNMR* 5.52 ppm              26   CH.sub.3                                                                                 ##STR51##                                                                                 ##STR52##      Melting point 103° C.       27   C.sub.2 H.sub.5                                                                         CH.sub.3                                                                                   ##STR53##      .sup.1 HNMR* 5.58 ppm              28   CH.sub.3(CH).sub.2                                                                      CH.sub.3                                                                                   ##STR54##      .sup.1 HNMR* 5.46 ppm              29   (CH.sub.3).sub.3 C                                                                      CH.sub.3                                                                                   ##STR55##      Melting point  61° C.       30                                                                                  ##STR56##                                                                              CH.sub.3                                                                                   ##STR57##      Melting point 88° C.        31                                                                                  ##STR58##                                                                              CH.sub.3                                                                                   ##STR59##      Melting point 78° C.        32   H         CH.sub.3                                                                                   ##STR60##      .sup.1 HNMR* 5.45 ppm              33   CH.sub.3  CH.sub.3                                                                                   ##STR61##      .sup.1 HNMR* 5.5 ppm               34   CH.sub.3  NCCH.sub.2CH.sub.2                                                                         ##STR62##      .sup.1 HNMR* 5.5 ppm               35   CH.sub.3  HOCH.sub.2CH.sub. 2                                                                        ##STR63##      .sup.1 HNMR* 5.5 ppm               36   H         H                                                                                          ##STR64##      Melting point 124-126              37   H         CH.sub.3                                                                                   ##STR65##      .sup.1 HNMR* 5.5 ppm               38   CH.sub.3  H                                                                                          ##STR66##      Melting point 163° C.       39   CH.sub.3  CH.sub.3                                                                                   ##STR67##      .sup.1 HNMR* 5.5 ppm               40   CH.sub.3  NCCH.sub.2                                                                                 ##STR68##      .sup.1 HNMR* 5.56 ppm              41   CH.sub.3  NCCH.sub.2CH.sub.2                                                                         ##STR69##      .sup.1 HNMR* 5.5 ppm               42   CH.sub.3                                                                                 ##STR70##                                                                                 ##STR71##      Melting point 108° C.       43   C.sub.2 H.sub.5                                                                         CH.sub.3                                                                                   ##STR72##      .sup.1 HNMR* 5.5 ppm               44   CH.sub.3 OCH.sub.2                                                                      NCCH.sub.2CH.sub.2                                                                         ##STR73##      .sup.1 HNMR* 5.6 ppm               45                                                                                  ##STR74##                                                                              CH.sub.3                                                                                   ##STR75##      .sup.1 HNMR* 5.53 ppm              46   CH.sub.3  CH.sub.3                                                                                   ##STR76##      .sup.1 HNMR* 5.28 ppm              47   CH.sub.3  CH.sub.3                                                                                   ##STR77##      Melting point 135°-140.d                                               egree. C.                          48   C.sub.2 H.sub.5                                                                         CH.sub.3                                                                                   ##STR78##      Melting point 133°-140.d                                               egree. C.                          49   CH.sub.3 OCH.sub.2                                                                      CH.sub.3                                                                                   ##STR79##      .sup.1 HNMR* 4.6 ppm               50                                                                                  ##STR80##                                                                              CH.sub.3                                                                                   ##STR81##      .sup.1 HNMR* 5.52 ppm              51   H         HOCH.sub.2CH.sub.2                                                                         ##STR82##      Melting point 118°-119.d                                               egree. C.                          52   CH.sub.3  CH.sub.3                                                                                   ##STR83##      .sup.1 HNMR* 5.66 ppm              53   CH.sub.3  NCCH.sub.2CH.sub.2                                                                         ##STR84##      .sup.1 HNMR* 5.66 ppm              54   C.sub.2 H.sub.5                                                                         CH.sub.3                                                                                   ##STR85##      Melting point 82° C.        55   CH.sub.3 OCH.sub.2                                                                      CH.sub.3                                                                                   ##STR86##      .sup.1 HNMR* 5.66 ppm              56   CH.sub.3 OCH.sub.2                                                                      NCCH.sub.2CH.sub.2                                                                         ##STR87##      Melting point 106° C.       57   CH.sub.3  (CH.sub.3).sub.3 C                                                                         ##STR88##      .sup.1 HNMR* 5.58 ppm              58   CH.sub.3                                                                                 ##STR89##                                                                                 ##STR90##      Melting point 98° C.        59   CH.sub.3                                                                                 ##STR91##                                                                                 ##STR92##      .sup.1 HNMR* 5.66 ppm              60   CH.sub.3                                                                                 ##STR93##                                                                                 ##STR94##      Melting point 98° C.        61   CH.sub.3                                                                                 ##STR95##                                                                                 ##STR96##      Melting point 160° C.       62   C.sub.2 H.sub.5                                                                         CH.sub.3                                                                                   ##STR97##      .sup.1 HNMR* 5.6 ppm               63                                                                                  ##STR98##                                                                              CH.sub.3                                                                                   ##STR99##      Melting point 75° C.        64   CH.sub.3(CH.sub.2).sub.2                                                                CH.sub.3                                                                                   ##STR100##     .sup.1 HNMR* 5.6 ppm               65   (CH.sub.3).sub.3 C                                                                      CH.sub.3                                                                                   ##STR101##     .sup.1 HNMR* 5.58 ppm              66   H         CH.sub.3                                                                                   ##STR102##     .sup.1 HNMR* 5.83 ppm              67   H         NCCH.sub.2CH.sub.2                                                                         ##STR103##     .sup.1 HNMR* 5.83 ppm              68   H         HOCH.sub.2CH.sub.2                                                                         ##STR104##     hu 1 HNMR* 5.83 ppm                69   CH.sub.3  H                                                                                          ##STR105##     Melting point 102° C.       70   CH.sub.3  CH.sub.3                                                                                   ##STR106##     .sup.1 HNMR* 5.83 ppm              71   CH.sub.3  NCCH.sub.2CH.sub.2                                                                         ##STR107##     .sup.1 HNMR* 5.83 ppm              72   CH.sub.3  HOCH.sub.2CH.sub.2                                                                         ##STR108##     Melting point 114°-116.d                                               egree. C.                          73   CH.sub.3 OCH.sub.2                                                                      NCCH.sub.2CH.sub.2                                                                         ##STR109##     .sup.1 HNMR* 5.91 ppm              74   H         H                                                                                          ##STR110##     Melting point 134° C.       75   H         CH.sub.3                                                                                   ##STR111##     .sup.1 HNMR* 5.66 ppm              76   CH.sub.3  H                                                                                          ##STR112##     Melting point 130°-132.d                                               egree. C.                          77   CH.sub.3  CH.sub.3                                                                                   ##STR113##     Melting point  110°-114.                                               degree. C.                         78   CH.sub.3  NCCH.sub.2                                                                                 ##STR114##     .sup.1 HNMR* 5.66 ppm              79   CH.sub.3  NCCH.sub.2CH.sub.2                                                                         ##STR115##     .sup.1 HNMR 5.66 ppm               80   CH.sub.3  HOCH.sub.2CH.sub.2                                                                         ##STR116##     .sup.1 HNMR* 5.66 ppm              81   H         H                                                                                          ##STR117##     Melting point 112°-115.d                                               egree. C.                          82   H         CH.sub.3                                                                                   ##STR118##     Melting point 115° C.       83   CH.sub.3  H                                                                                          ##STR119##     Melting point 160° C.       84   CH.sub.3  CH.sub.3                                                                                   ##STR120##     .sup.1 HNMR* 5.66 ppm              85   CH.sub.3  NCCH.sub.2                                                                                 ##STR121##     .sup.1 HNMR* 5.7 ppm               86   CH.sub.3  NCCH.sub.2CH.sub.2                                                                         ##STR122##     .sup.1 HNMR* 5.66 ppm              87   CH.sub.3  HOCH.sub.2CH.sub.2                                                                         ##STR123##     Melting point 146°-147.d                                               egree. C.                          88   CH.sub.3  H                                                                                          ##STR124##     Melting point  104° C.      89   CH.sub.3  CH.sub.3                                                                                   ##STR125##     .sup.1 HNMR* 5.5 ppm               90   CH.sub.3  (CH.sub.3).sub.3 C                                                                         ##STR126##     .sup.1 HNMR* 5.5 ppm               91   CH.sub.3  NCCH.sub.2                                                                                 ##STR127##     Melting point 81° C.        92   CH.sub.3  NCCH.sub.2CH.sub.2                                                                         ##STR128##     Melting point 82° C.        93   CH.sub.3  HOCH.sub.2CH.sub.2                                                                         ##STR129##     .sup.1 HNMR* 5.5 ppm               94   CH.sub.3                                                                                 ##STR130##                                                                                ##STR131##     .sup.1 HNMR* 5.5 ppm               95   C.sub.2 H.sub.5                                                                         CH.sub.3                                                                                   ##STR132##     .sup.1 HNMR* 5.53 ppm              96   CH.sub.3 OCH.sub.2                                                                      CH.sub.3                                                                                   ##STR133##     .sup.1 HNMR* 5.53 ppm              97   CH.sub.3 OCH.sub.2                                                                      NCCH.sub.2CH.sub.2                                                                         ##STR134##     .sup.1 HNMR* 5.53 ppm              98                                                                                  ##STR135##                                                                             CH.sub.3                                                                                   ##STR136##     Melting point 119° C.       99   H         NC CH.sub.2CH.sub.2                                                                        ##STR137##     Melting point 116° C.       100  CH.sub.3  H                                                                                          ##STR138##     .sup.1 HNMR* 5.63 ppm              101  CH.sub.3  CH.sub.3                                                                                   ##STR139##     Melting point 91° C.        102  CH.sub.3  NCCH.sub.2                                                                                 ##STR140##     Melting point 130° C.       103  CH.sub.3  NCCH.sub.2CH.sub.2                                                                         ##STR141##     Melting point 97° C.        104  CH.sub.3  HOCH.sub.2CH.sub.2                                                                         ##STR142##     Melting point 94°  C.       105  CH.sub.3                                                                                 ##STR143##                                                                                ##STR144##     .sup.1 HNMR* 5.65 ppm              106  CH.sub.3                                                                                 ##STR145##                                                                                ##STR146##     .sup.1 HNMR* 5.6 ppm               107  CH.sub.3 OCH.sub.2                                                                      CH.sub.3                                                                                   ##STR147##     .sup.1 HNMR* 5.66 ppm              108  CH.sub.3 OCH.sub.2                                                                      NCCH.sub.2CH.sub.2                                                                         ##STR148##     .sup.1 HNMR* 5.66 ppm              109                                                                                 ##STR149##                                                                             CH.sub.3                                                                                   ##STR150##     Melting point 95° C.        110  H         CH.sub.3                                                                                   ##STR151##     .sup.1 HNMR* 5.5 ppm               111  CH.sub.3  H                                                                                          ##STR152##     Melting point 154°-156.d                                               egree. C.                          112  CH.sub.3  CH.sub.3                                                                                   ##STR153##     Melting point 108°-110.d                                               egree. C.                          113  CH.sub.3  NCCH.sub.2CH.sub.2                                                                         ##STR154##     .sup.1 HNMR* 5.5 ppm               114  CH.sub.3  HOCH.sub.2CH.sub.2                                                                         ##STR155##     Melting point 91° C.        115  H         CH.sub.3                                                                                   ##STR156##     .sup.1 HNMR* 5.5 ppm               116  CH.sub.3  H                                                                                          ##STR157##     Melting point 116° C.       117  CH.sub.3  CH.sub.3                                                                                   ##STR158##     .sup.1 HNMR* 5.5 ppm               118  CH.sub.3  NCCH.sub.2CH.sub.2                                                                         ##STR159##     .sup.1 HNMR* 5.5 ppm               119  CH.sub.3  HOCH.sub.2CH.sub.2                                                                         ##STR160##     .sup.1 HNMR* 5.5 ppm               120  H         H                                                                                          ##STR161##     Melting point 80° C.        121  H         CH.sub.3                                                                                   ##STR162##     .sup.1 HNMR* 5.43 ppm              122  H         NCCH.sub.2CH.sub.2                                                                         ##STR163##     .sup.1 HNMR* 5.5 ppm               123  CH.sub.3  H                                                                                          ##STR164##     Melting point 120° C.       124  CH.sub.3  CH.sub.3                                                                                   ##STR165##     Melting point 64°-66.deg                                               ree. C.                            125  CH.sub.3  NCCH.sub.2                                                                                 ##STR166##     .sup.1 HNMR* 5.5 ppm               126  CH.sub.3  NCCH.sub.2CH.sub.2                                                                         ##STR167##     .sup.1 HNMR* 5.43 ppm              127  CH.sub.3  HOCH.sub.2CH.sub.2                                                                         ##STR168##     Melting point 94°-96.deg                                               ree. C.                            128  H         CH.sub.3                                                                                   ##STR169##     .sup.1 HNMR* 5.5 ppm               129  CH.sub.3  H                                                                                          ##STR170##     Melting point 120-122°                                                 C.                                 130  CH.sub.3  CH.sub.3                                                                                   ##STR171##     Melting point 65° C.        131  CH.sub.3  NCCH.sub.2                                                                                 ##STR172##     .sup.1 HNMR* 5.5 ppm               132  CH.sub.3  CH.sub.3                                                                                   ##STR173##     .sup.1 HNMR* 4.55 ppm              133  CH.sub.3  H                                                                                          ##STR174##     Melting point >150° C.                                                 (decomposition)                    134  CH.sub.3  CH.sub.3                                                                                   ##STR175##     Melting point 80-82°                                                   C.                                 135  CH.sub.3  CH.sub.3 OCOCH.sub.2                                                                       ##STR176##     .sup.1 HNMR* 5.6 ppm               136  CH.sub.3  CH.sub.3 OCOCH.sub.2                                                                       ##STR177##     .sup.1 HNMR* 5.6 ppm               137  CH.sub.3  CH.sub.3                                                                                   ##STR178##     .sup.1 HNMR* 5.8 ppm               138  CH.sub.3  CH.sub.3                                                                                   ##STR179##     Melting point >150° C.                                                 (decomposition)                    139  CH.sub.3  H                                                                                          ##STR180##     Melting point 160°-165.d                                               egree.                             140  CH.sub.3  CH.sub.3                                                                                   ##STR181##     Melting point 168° C.       141  CH.sub.3  NCCH.sub.2CH.sub.2                                                                         ##STR182##     Melting point 150° C.       142  CH.sub.3                                                                                 ##STR183##                                                                                ##STR184##     Melting point 140°-145.d                                               egree.  C.                         143  CH.sub.3                                                                                 ##STR185##                                                                                ##STR186##     Melting point 182° C.       144  C.sub.2 H.sub.5                                                                         CH.sub.3                                                                                   ##STR187##     Melting point 177° C.       145  CH.sub.3 OCH.sub.2                                                                      CH.sub.3                                                                                   ##STR188##     Melting point 165°-175.d                                               egree. C.                          146  C.sub.2 H.sub.5 OCH.sub.2                                                               CH.sub.3                                                                                   ##STR189##     Melting point 138°-145.d                                               egree. C.                          147  CH.sub.3 SCH.sub.2                                                                      CH.sub.3                                                                                   ##STR190##     .sup.1 HNMR* 5.95 ppm              148                                                                                 ##STR191##                                                                             CH.sub.3                                                                                   ##STR192##     Melting point 111° C.       149  H         H                                                                                          ##STR193##     Melting point 184°-186.d                                               egree. C.                          150  H         CH.sub.3                                                                                   ##STR194##     Melting point 90° C.        151  H         NCCH.sub.2CH.sub.2                                                                         ##STR195##     Melting point 172°-176.d                                               egree. C.                          152  CH.sub.3  H                                                                                          ##STR196##     Melting point 206° C.       153  CH.sub.3  CH.sub.3                                                                                   ##STR197##     Melting point 177°-179.d                                               egree. C.                          154  CH.sub.3  (CH.sub.3).sub.3 C                                                                         ##STR198##     .sup.1 HNMR* 6.0 ppm               155  CH.sub.3  NCCH.sub.2CH.sub.2                                                                         ##STR199##     Melting point 176° C.       156  CH.sub.3  HOCH.sub.2CH.sub.2                                                                         ##STR200##     .sup.1 HNMR* 6.0 ppm               157  CH.sub.3                                                                                 ##STR201##                                                                                ##STR202##     .sup.1 HNMR* 6.05 ppm              158  CH.sub.3                                                                                 ##STR203##                                                                                ##STR204##     Melting point 210° C.       159  CH.sub.3                                                                                 ##STR205##                                                                                ##STR206##     Melting point 148° C.       160  C.sub.2 H.sub.5                                                                         H                                                                                          ##STR207##     Melting point 173°          161  C.sub.2 H.sub.5                                                                         CH.sub.3                                                                                   ##STR208##     Melting point 142°-142-1                                               44° C.                      162  CH.sub.3(CH.sub.2).sub.2                                                                H                                                                                          ##STR209##     Melting point 100° C.       163  CH.sub.3(CH.sub.2 ).sub.3                                                               H                                                                                          ##STR210##     Melting point 110° C.       164  CH.sub.3(CH.sub.2).sub.3                                                                CH.sub.3                                                                                   ##STR211##     Melting point 105° C.       165  (CH.sub.3).sub.3 C                                                                      CH.sub.3                                                                                   ##STR212##     Melting point 190° C.       166  CH.sub.3 OCH.sub.2                                                                      CH.sub.3                                                                                   ##STR213##     Melting point 128° C.       167  CH.sub.3 OCH.sub.2                                                                      NCCH.sub.2CH.sub.2                                                                         ##STR214##     .sup.1 HNMR* 6.12 ppm              168                                                                                 ##STR215##                                                                             CH.sub.3                                                                                   ##STR216##     .sup.1 HNMR* 6.06 ppm              169                                                                                 ##STR217##                                                                             CH.sub.3                                                                                   ##STR218##     Melting point 196°-198.d                                               egree. C.                          170  CH.sub.3                                                                                 ##STR219##                                                                                ##STR220##     .sup.1 HNMR* 5.4 ppm               171  CH.sub.3  CH.sub.2CHCH.sub.2                                                                         ##STR221##     .sup.1 HNMR* 5.35 ppm              172  CH.sub.3  HCCCH.sub.2                                                                                ##STR222##     .sup.1 HNMR* 5.4 ppm               173  CH.sub.3  C.sub.2 H.sub.5 O COCH.sub.2                                                               ##STR223##     .sup.1 HNMR* 5.4 ppm               174  CH.sub.3                                                                                 ##STR224##                                                                                ##STR225##     Melting point 162° C.       175  CH.sub.3                                                                                 ##STR226##                                                                                ##STR227##     .sup.1 H-NMR* 5.3 ppm              176  CH.sub.3                                                                                 ##STR228##                                                                                ##STR229##     Melting point 149° C.       177  CH.sub.3                                                                                 ##STR230##                                                                                ##STR231##     .sup.1 HNMR* 5.4 ppm               178  CH.sub.3  CH.sub.3 OCOCH.sub.2                                                                       ##STR232##     .sup.1 HNMR* 5.3 ppm               179  CH.sub.3                                                                                 ##STR233##                                                                                ##STR234##     .sup.1 HNMR* 5.45 ppm              180  CH.sub.3  CH.sub.2 OH                                                                                ##STR235##     .sup.1 HNMR* 5.3 ppm               181  H         CH.sub.2 COCH.sub.3                                                                        ##STR236##     Melting Point 114° C.       182  H         CH.sub.2 CH.sub.2 OH                                                                       ##STR237##     .sup.1 HNMR* 5.5                   __________________________________________________________________________                                               PPM                                 *The .sup.1 HNMR spectra were recorded in CDCl.sub.3 with                     tetramethylsilane as the internal standard. As a rule the chemical shifts     are stated as δ values for the grouping                                 ##STR238##                                                                    -                                                                        

Preparation of the precursors of the formula (IV) Example IV-1##STR239##

140 ml (1 mole) of triethylamine are added dropwise to 146 g (1 mole) ofethyl 2-hydroximino-3-oxo-butyrate [compare, for example, Helv. Chem.Acta. 67, 906-915 (1984)] and 159 g (1 mole) of3-ethyl-5-chloromethylisoxazole in 600 ml of acetonitrile at roomtemperature, while stirring, and, when the addition has ended, themixture is stirred at 50° C. for a further 6 hours. For working up, thetriethylamine hydrochloride which has precipitated out is filtered offand the solvent is then removed in vacuo. The residue is taken up inmethylene chloride, the mixture is washed several times with water,dried over sodium sulphate and concentrated in vacuo and the residue isdistilled under a high vacuum.

157 g (59% of theory) of ethylβ-keto-α-[(3-ethylisoxazol-5-yl)-methoximino]-butyrate of boiling point80° to 160° C./1.5 mbar are obtained.

The following alkoximinocarboxylic acid esters of the general formula(IV) are obtained in a corresponding manner and in accordance with thegeneral statements on the preparation: ##STR240##

                  TABLE 2                                                         ______________________________________                                        Example                             Physical                                  No.    R.sup.1 R.sup.2 Het          data                                      ______________________________________                                        IV-2   CH.sub.3                                                                              C.sub.2 H.sub.5                                                                                    .sup.1 HNMR* 5.33 ppm                     IV-3   CH.sub.3                                                                              C.sub.2 H.sub.5                                                                        ##STR241##  n.sub.D.sup.20 : 1.5321                   ______________________________________                                         *Same as footnote Table 1                                                

Use Examples

The compound shown below was employed as the comparison substance in theuse examples which follow: ##STR242##

Example A

Phytophthora Test (tomato)/protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dripping wet. After the spraycoating has dried on, the plants are inoculated with an aqueous sporesuspension of Phytophthora infestans.

The plants are placed in an incubation cabinet 100% relative atmospherichumidity and at about 20° C.

Evaluation is carried out 3 days after the inoculation.

In this test, a clearly superior activity compared with the prior art isshown, for example, by the compounds according to preparation Examples1, 5, 58, 68, 102, 103, 140.

Example B

Leptosphaeria nodorum test (wheat)/protective

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dew-moist. After the spray coatinghas dried on, the plants are sprayed with a conidia suspension ofLeptosphaeria nodorum. The plants remain for 48 hours in an incubationcabinet at 20° C. and 100% relative atmospheric humidity.

The plants are placed in a greenhouse at a temperature of about 15° C.and a relative atmospheric humidity of about 80%.

Evaluation is effected 10 days after the inoculation.

In this test, a clearly superior activity compared with the prior art isshown, for example, by the compounds according to the followingpreparation examples: 3, 27, 43, 104, 110, 115, 116, 118, 119 and 132.

Example C

Pyricularia test (rice)/protective

Solvent: 12.5 parts by weight of acetone

Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether.

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, and theconcentrate is diluted with water and the stated amount of emulsifier,to the desired concentration.

To test for protective activity, young rice plants are sprayed with thepreparation of active compound until dripping wet. After the spraycoating has dried on, the plants are inoculated with an aqueous sporesuspension of Pyricularia oryzae. The plants are then placed in agreenhouse at 100% relative atmospheric humidity and 25° C.

Evaluation of the disease infestation is carried out 4 days after theinoculation.

In this test, a clearly superior activity compared with the prior art isshown, for example, by the compounds according to preparation Examples5, 47, 67, 101, 103, 104, 106, 116, 118, 120, 123, 126, 127, 129, 140,150 and 153.

Example D

Pyricularia test (rice)/systemic

Solvent: 12.5 parts by weight of acetone

Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether.

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, and theconcentrate is diluted with water and the stated amount of emulsifier,to the desired concentration.

To test for systemic properties, standard soil in which young riceplants have been grown is watered with 40 ml of the preparation ofactive compound. 7 days after the treatment, the plants are inoculatedwith an aqueous spore suspension of Pyricularia oryzae. Thereafter, theplants remain in a greenhouse at a temperature of 25° C. and a relativeatmospheric humidity of 100% until they are evaluated.

Evaluation of the disease infestation is carried out 4 days after theinoculation.

In this test, a clearly superior activity compared with the prior art isshown, for example, by the compounds according to the followingpreparation examples: 5, 7, 8, 14, 15, 16, 150 and 153.

It is understood that the specification and examples are illustrativebut not limitative of the present invention and that other embodimentswithin the spirit and scope of the invention will suggest themselves tothose skilled in the art.

We claim:
 1. An alkoxyiminocarboxylic acid ester of the formula##STR243## in which R represents alkyl,R¹ represents hydrogen, alkyl,alkenyl, alkinyl, cyanoalkyl, hydroxyalkyl, alkoxyalkyl, alkylthioalkyl,alkoxycarbonyl, hydroxycarbonylalkyl, alkoxycarbonylalkyl,aminocarbonylalkyl, alkylaminocarbonylalkyl or dialkylaminocarbonylalkylor in each case optionally substituted oxiranylalkyl, aralkyl,heterocyclyl or aryl and Het represents an optionally substitutedheterocyclic radical of the formula ##STR244## or ##STR245## wherein Xin each case represents oxygen or sulphur.
 2. A compound according toclaim 1 of the formula ##STR246##
 3. A compound according to claim 1 ofthe formula ##STR247##